Compositions of metal oxide semiconductor nanomaterials and hemostatic polymers

ABSTRACT

The present invention provides composition comprising a metal oxide semiconductor nanomaterial coated or dispersed with a hemostatic polymer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.16/582,529, filed on Sep. 25, 2019 which is hereby incorporated byreference in their entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to hemostatic polymers coatedor adhered on metal oxide semiconductor nanomaterials.

BACKGROUND OF THE INVENTION

Metal oxide semiconductor nanomaterials and especially copper oxide(CuO) and zinc oxide (ZnO) nanomaterials (Cu_(1-x)/Zn_(x)O) have beenpreviously reported possessing antibacterial, antimicrobial, andantifungal properties. Hemostatic polymers are widely known to coagulateblood through various mechanisms. Coating or adhering a hemostaticpolymer onto the surface of the metal oxide semiconductor nanomaterialwould provide not only antibacterial, antimicrobial, and antifungalproperties but also provide coagulation properties.

What is needed are improved compositions comprising metal oxidesemiconductor nanomaterials which exhibit many beneficial propertieswhich are coated or adhered to a hemostatic polymer to provideadditional coagulation properties.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 is a chemical scheme for the nanoparticle preparation. The schemedemonstrates preparation and precipitation of Aurichalcite precursor inthe first step; the dehydration of the Aurichalcite precursor in step 2;and thermal decomposition of the Aurichalcite precursor to metal oxideto form the metal oxide semiconductor nanomaterials in step 3.

FIG. 2 is a comparison of the XRD diffractograms for pure CuO andCuO_(1-X)/ZnO_(X). The diffractograms show the shift for somediffraction signals related to ZnO faces.

FIG. 3 is a comparison of Raman spectra for pure CuO, regular Zn dopedCuO, and CuO_(1-X)/ZnO_(X). From this comparison, the loss of symmetryon the whole structure (broad signals), new peaks related with thepresence of O—Zn—O clusters, and probable presence of heterojunction dueto the increment of multiphoton mode MP that is evidence of anisotropicconduction of electrons is shown.

FIG. 4 is a High-resolution transmission electron microscopy (HR-TEM)with EDS detection for Zn and Cu which shows a non-homogenousdistribution of those components and a clear core/shell structure.

FIG. 5 shows the optical band gap E_(g) calculation from the UV-visspectrum of the metal oxide nanomaterials.

FIG. 6 is a representation showing the bactericidal activity against E.coli in saline and 5% fetal bovine serum (FBS) to simulate the woundfluid conditions according to ISO requirement. In both cases, within onehour of exposure, a total elimination of the E. coli in saline and 5%fetal bovine serum (FBS) was seen.

FIG. 7 shows a picture of a hemostatic polymer coated on theCuO_(1-X)/ZnO_(X).

SUMMARY OF THE INVENTION

One aspect of the present disclosure encompasses a metal oxidesemiconductor nanomaterial composition comprising a metal oxidenanomaterial and at least one hemostatic polymer wherein the metal oxideA and the metal oxide B are independently selected from a groupcomprising an alkaline earth metal, a d-block transition metal, f-blockmetal or combinations thereof; wherein the nanomaterial comprisesclusters of metal oxide quantum dots, and wherein the hemostatic polymeris adhered or coated on the metal oxide semiconductor nanomaterial.

Another aspect of the present disclosure encompasses a metal oxidesemiconductor nanomaterial composition comprising a metal oxidenanomaterial and at least one hemostatic polymer; wherein the metalportion of metal oxide A and the metal portion of metal oxide B areindependently selected from a group consisting titanium, manganese,nickel, silver, calcium, magnesium, zinc, copper, or combinationsthereof; wherein the nanomaterial comprises of clusters of metal oxidequantum dots; and wherein the hemostatic polymer is adhered or coated onthe metal oxide semiconductor nanomaterial.

Still another aspect of the present disclosure encompasses a metal oxidesemiconductor nanomaterial composition comprising a CuO and ZnOnanomaterial and at least one hemostatic polymer wherein thenanomaterial comprises clusters of CuO and ZnO quantum dots comprisingheterojunctions comprise at least one n-type metal oxide nanoparticleand at least one p-type metal oxide nanoparticle; and wherein thehemostatic polymer is adhered or coated on the metal oxide semiconductornanomaterial.

Other features and iterations of the invention are described in moredetail below.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, disclosed herein, are compositions of a metal oxidesemiconductor nanomaterial composition comprising a metal oxidenanomaterial and at least one hemostatic polymer wherein the metal oxidesemiconductor nanomaterial composition comprises metal oxide A and themetal oxide B are independently selected from a group comprising analkaline earth metal, a d-block transition metal, f-block metal orcombinations thereof; wherein the nanomaterial comprises clusters ofmetal oxide quantum dots, and wherein the hemostatic polymer is adheredor coated on the metal oxide semiconductor nanomaterial Thesecombinations of metal oxides semiconductor nanomaterial and thehemostatic polymer provide many beneficial attributes such as a narrowoptical band-gap, inhomogeneous electrical conductivity, a porousstructure, relatively large surface area per unit of mass, a largesurface area per unit of volume, and coagulation properties. Thenanomaterials additionally release reactive oxygen species such thatthese nanomaterials exhibit antimicrobial properties, antibacterialproperties, antifungal properties, or combinations thereof.

(I) Composition

The metal oxide semiconductor nanomaterial, described below, comprisesat least two metal oxides, metal oxide A and metal oxide B. Thesenanomaterials comprise clusters of metal oxide quantum dots.

(a) Metal Oxide Semiconductor Nanomaterial

The metal oxide semiconductor nanomaterial comprises a metal oxide A anda metal oxide B wherein the nanomaterial are clusters of metal oxidequantum dots.

A wide variety of metal oxides may be used as metal oxide A and metaloxide B. In various embodiments, metal oxide A and metal oxide whereinthe metal portion of metal oxide A and the metal portion of metal oxideB are independently selected from a group comprising an alkaline earthmetal, a d-transition metal, f-transition, or combinations thereof.Non-limiting examples of suitable metal portion of alkaline earth metaloxides may be beryllium, magnesium, calcium, strontium, or barium.Non-limiting examples of the metal portion of suitable transition metaloxides may be scandium, titanium vanadium, chromium, manganese, iron,cobalt, nickel, copper, yttrium, zirconium, platinum, gold, mercury,niobium, iridium, molybdenum, technetium, ruthenium, rhodium, palladium,silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, anylanthanide or zinc.

In preferred embodiments, metal oxide A and metal oxide B wherein themetal portion of metal oxide A and the metal portion of metal oxide Bare independently selected from a group consisting of titanium,manganese, nickel, silver, calcium, magnesium, zinc, copper, orcombinations thereof.

In particularly preferred embodiments, metal oxide A and metal oxide Bwherein the metal portion of metal oxide A and the metal portion ofmetal oxide B are independently selected from a group consisting ofzinc, copper, or combinations thereof. The copper-zinc mixed oxidenanomaterial has a chemical formula of Cu_(1-x)O/ZnO_(x), wherein x isthe atomic ratio of the zinc oxide impurities on the nanomaterial.Generally, the value of x may range from about 0.01 to about 0.26. Invarious, the value of X may range from about 0.01 to about 0.26, or fromabout 0.03 to about 0.24. In a preferred embodiment, the value of x maybe around 0.2.

The crystalline structure of the copper oxide and/or the copper-zincmixed oxide Cu_(1-x)O/Zn_(x)O is modified tenorite. In the modifiedtenorite structure, zinc oxide clusters may intercalate some of copperoxide crystal lattice as interstitial impurities. Tenorite is thecrystal structure of copper oxide CuO.

The crystal structure of the metal oxide can be determined by methodknown in the art. Non-limiting methods for determination of the crystalstructure may be Raman spectrometry, high resolution transition electronmicroscopy (HR-TEM/EDS), x-ray crystallography, or combinations thereof.

As appreciated by the skilled artisan, the nanomaterial comprises tworegions, where one region is the surface region and the second region isthe core region of the nanomaterial. Preferably, the surface region ofthe nanomaterial completely encloses the core region of thenanomaterial. The distribution of these metal oxides can and will vary.In one embodiment, metal oxide A is substantially distributed in thecore region of the nanomaterial while metal oxide B is substantiallydistributed in the surface region. In another embodiment, metal oxide Ais substantially distributed in the surface region of the nanomaterialwhile metal oxide B is substantially distributed in the core region.

In various embodiments, metal oxide A is substantially distributed inthe core region of the nanomaterial while metal oxide B is substantiallydistributed in the surface region. Generally, the surface regioncomprises more than 10% by weight of metal oxide B and less than 90% byweight of metal oxide A. In various embodiments, the surface regioncomprises more than 10% by weight, more than 20% by weight, or more than25 weight % of metal oxide B. The core region comprises less than 90% byweight of metal oxide A. In various embodiments, the core regioncomprises less than 90% by weight, less than 80% by weight, or less than75% by weight of metal oxide A. In a preferred embodiment, the surfaceregion comprises about 27%±3% by weight of metal oxide B and the coreregion comprises 73%±3% by weight of metal oxide A.

In other embodiments, metal oxide A is substantially distributed in thesurface region of the nanomaterial while metal oxide B is substantiallydistributed in the core region. In general, the surface region comprisesmore than 80% by weight of metal oxide A. In various embodiments, thesurface region comprises more than 80% by weight, more than 85% byweight, or more than 90% by weight of metal oxide A. The core regioncomprises less than 20% by weight of metal oxide B. In variousembodiments, the core region comprises less than 20% by weight, lessthan 15% by weight, or less than 10% by weight. In a preferredembodiment, the surface region comprises about 93%±1% of metal oxide Aand the core region comprises about 9%+1% of metal oxide B.

The distribution of the metal oxide B and metal oxide A in the metaloxide semiconductor nanomaterial may be determined by characterizationmethods known in the art. Non-limiting examples of suitablecharacterization methods may be scanning electron microscopy (SEM),energy-dispersion X-ray spectroscopy (EDS), transmission electronmicroscopy (TEM), or combination thereof.

As appreciated by the skilled artisan, a mixture of the nanomaterialsmay be present in the composition. Overall, the mass content of metaloxide B in the nanomaterial may range from about 10% by weight to about30% by weight. In various embodiments, the mass content of metal oxide Bin the nanomaterial may range from about 10% to about 30% by weight orfrom about 15% by weight to about 25% by weight. In a preferredembodiment, the mass content of metal oxide B in the nanomaterial may beabout 18%±4% by weight.

The metal oxide nanomaterial is a semiconductor. The semiconductorcomprises at least one n-type metal oxide nanoparticle and at least onep-type nanoparticle. As appreciated by the skilled artisan, an n-typemetal oxide is a semiconductor metal oxide in which most charge carriersare electrons, whereas a p-type metal oxide is a semiconductor metaloxide in which most charge carriers are electron holes. Preferably, themetal oxide semiconductor nanomaterial comprises heterojunctions unionsbetween the n-type and the p-type semiconductors. As appreciated by theskilled artisan, heterojunctions are interfaces between two dissimilarcrystalline semiconductors which have unequal band gaps.

The metal oxide semiconductor nanomaterial shows an inhomogeneouselectrical conductivity. The inhomogeneous electrical conductivity maybe the result of an inhomogeneous distribution of the metal oxide B inthe surface region of the metal oxide semiconductor nanomaterial or maybe result from an inhomogeneous distribution of the metal oxide A in thesurface region of the metal oxide semiconductor nanomaterial.

Quantum dots exhibit properties that are an intermediate between thoseof bulk semiconductors and those of discrete atoms or molecules. Quantumdots are very small semiconductor particles having nanometer size.Quantum dots are also semiconductor nanocrystals. The semiconductornanomaterials of the present invention comprise semiconductor particlesof nanometer size, nanocrystals, or combinations thereof. In otherwords, any semiconductor metal oxide may be synthesized as quantum dots.

(b) Hemostatic Polymer Material, Organic Molecule, or CombinationsThereof

The metal oxide semiconductor nanomaterial may further comprise at leastone polymer material, at least one organic molecule, or combinationsthereof. In some embodiments, the nanomaterial may be dispersed in theat least one polymer, at least one organic molecule, or combinationsthereof. In other embodiments, the metal oxide at the surface of thenanomaterial may be functionalized with the at least one polymer, atleast one organic molecule, or combinations thereof. In either case, themetal oxide semiconductor nanomaterial may be used in many differentapplications and environments.

A wide variety of polymer materials and organic molecules may be usedwith the metal oxide nanomaterial. Non-limiting examples of suitablepolymer materials may be chitosan, alginate, gelatin, carboxymethylcellulose, polyethylene glycol, or combinations thereof. Non-limitingexamples of suitable organic molecules may be octadecanethiol,perfluorothiol, cysteine, mercaptoalkanes, citric acid, oleic acid, orcombinations thereof. In one preferred embodiment, the at least onepolymer is a hemostatic polymer. Non-limiting examples of hemostaticpolymers may be chitosan, alginate, gelatin, carboxymethyl cellulose,polyethylene glycol, collagen, alginic acid, poly(cyanacrylate)s,(polyalkylene oxide)s, or salts thereof.

Generally, the weight % (wt %) of the at least one polymer material, atleast one organic molecule, or combinations thereof dispersed orfunctionalized on the metal oxide semiconductor nanomaterial may rangefrom about 1 wt % to about 5 wt %. In various embodiments, the weight %(wt %) of the at least one polymer material, at least one organicmolecule, or combinations thereof dispersed or functionalized on themetal oxide semiconductor nanomaterial may range from about 1 wt % toabout 5 wt %, from about 2 wt % to about 4 wt %, or from about 2.5 wt %to about 3.5 wt %. In one preferred embodiment, the weight % (wt %) ofthe at least one polymer material, at least one organic molecule, orcombinations thereof dispersed or functionalized on the metal oxidesemiconductor nanomaterial may be about 3 wt %.

In general, the thickness of the at least one polymer, at least oneorganic molecule, or combinations thereof may range from about 1.0 nm toabout 10.0 nm. In various embodiments, the thickness of the at least onepolymer, at least one organic molecule, or combinations thereof mayrange from about 1.0 nm to about 10.0 nm, from about 2.0 nm to about 8.0nm, or from about 3.0 to about 6.0 nm.

(c) Properties of the Metal Oxide Semiconductor Nanomaterial

The nanomaterial, as described above, exhibits many useful and uniqueproperties.

Generally, the optical band gap of the metal oxide semiconductornanomaterial may range from about 0.5 eV to 6.5 eV. In variousembodiments, the optical band gap of the metal oxide semiconductornanomaterial may range from about 0.5 eV to 6.5 eV, from about 1.0 eV to4.0 eV, from about 1.2 eV to 2.1 eV, or from about 1.74 eV to 1.85 eV.In a preferred embodiment, the optical band gap of the metal oxidesemiconductor nanomaterial may be about 1.8 eV.

The metal oxide semiconductor nanomaterial comprises a mesoporousstructure at a nanometer scale, a large surface area per unit of mass(m²/g), a large surface area per unit of volume (m²/mL), or combinationsthereof. Generally, the surface area of the metal oxide semiconductornanomaterial may be larger than 20 m²/g. In various embodiments, thesurface area of the metal oxide semiconductor nanomaterial may be largerthan about 20 m²/g, or larger than about 40 m²/g. In a preferredembodiment, the surface area of the metal oxide semiconductornanomaterial may range from about 40 m²/g.

Generally, the size of or at least one dimension of metal oxidesemiconductor nanoparticle may range from about 1 nanometers to 10,000nanometers. In various embodiments, the size of or at least onedimension of metal oxide semiconductor nanoparticle may range from about1 nanometer to 10,000 nanometers, from about 10 nanometers to about5,000 nanometers, or from about 100 nanometers to about 1,000nanometers. In one embodiment, the size of or at least one dimension ofmetal oxide semiconductor nanoparticle may range from about 10nanometers to 1,000 nanometers. In a preferred embodiment, the size ofor at least one dimension of metal oxide semiconductor nanoparticle mayrange from about 10 nanometers to about 150 nanometers.

In general, the thickness of the surface region may range from about 1nm to about 1000 nm. In various embodiments, the thickness of thesurface area may range from about 1 nm to about 1000 nm, from about 10nm to about 50 nm, or from about 15 nm to about 45 nm. In a preferredembodiment, the thickness of the surface area may be about 30 nm.

The metal oxide semiconductor nanomaterial exhibits antimicrobialproperties, antibacterial properties, antifungal properties, or acombination thereof. These metal oxide semiconductor nanomaterialsrelease reactive oxygen species once in contact with a microorganism, abacterium, or a fungus. Non-limiting examples of reactive oxygen speciesmay be oxygen, a superoxide anion, a peroxide anion, a hydroxyl radical,or combinations thereof. These reactive oxygen species, once in contactwith a microorganism, a bacterium, or a fungus can cause damage to cellsthrough oxidative damage. These metal oxide semiconductor nanomaterialspresent positively charge surface, which might interact with thenegatively charged bacterial membrane and cause physical damage andmembrane permeability disruption by electrostatic interactions with themicroorganism.

The antimicrobial properties, antibacterial properties, antifungalproperties, or a combination thereof of the metal oxide semiconductornanomaterials is defined as a bactericidal effect expressed aspercentage of mortality against a specific kind of bacteria for aspecific duration of time in a specific concentration. Generally, theaverage of mortality rate of the nanomaterial against Escherichia coliover from 1 to 24 hour time period may be larger than about 50%. Invarious embodiments, the average mortality rate of the nanomaterialagainst Escherichia coli over an hour time period may be larger thanabout 90%, larger than about 95%, larger than 99%, larger than about99.9%, or larger than 99.99%. In a preferred embodiment, the averagemortality rate of the nanomaterial against Escherichia coli over an hourtime period may be larger than about 99.99%.

The coated or adhered metal oxide semiconductor nanomaterial with atleast one polymer, at least one organic molecule, or combinationsthereof exhibit unique properties. In one preferred embodiment, the atleast one polymer, at least one organic molecule, or combinationsthereof may be a hemostatic polymer. Specific hemostatic polymers aredescribed above. The hemostatic polymer provides additional attributessuch as blood coagulation.

The surface ζ-potential for 100 ppm water suspension of chitosanfunctionalized or coated on the metal oxide semiconductor nanomaterialmay range from +10 mV to about +30 mV. In various embodiments, thesurface ζ-potential for 100 ppm water suspension of chitosanfunctionalized or coated on the metal oxide semiconductor nanomaterialmay range from +10 mV to about +30 mV, from about +15 mV to about +25mV, or about +20 mV.

The surface ζ-potential for 100 ppm water suspension of calcium alginatefunctionalized or coated on the metal oxide semiconductor nanomaterialmay range from −40 mV to about 0 mV. In various embodiments, the surfaceζ-potential for 100 ppm water suspension of calcium alginatefunctionalized or coated on the metal oxide semiconductor nanomaterialmay range from −40 mV to about 0 mV, from about −30 mV to about −10 mV,or about −20 mV.

The antimicrobial activity for the hemostatic polymer coated or adheredon the metal oxide semiconductor nanomaterial in a 40 ppm suspension ofEscherichia coli may be at least 95%. In various embodiments, theantimicrobial activity for the hemostatic polymer dispersed orfunctionalized on the metal oxide semiconductor nanomaterial in a 40 ppmsuspension of Escherichia coli may be at least 95%, at least 97.5%, atleast 99%, or at least 99.999%. In one preferred embodiment, theantimicrobial activity for the hemostatic polymer coated or adhered onthe metal oxide semiconductor nanomaterial in a 40 ppm suspension ofEscherichia coli is at least 99.999% or not less than a 5 log reduction.

(II) Processes for Preparing the Metal Oxide Semiconductor Nanomaterial

In another aspect, disclosed herein, are processes to prepare the metaloxide semiconductor nanomaterial. The process comprises: (a) providing afirst aqueous solution comprising a soluble metal salt A and a solublemetal salt B; (b) providing a second aqueous solution comprising atleast one soluble anion; (c) admixing the second aqueous solution withthe first aqueous solution to form an insoluble precursor metal oxidesemiconductor nanomaterial; (d) isolating the metal oxide semiconductornanomaterial precursor; (e) drying the metal oxide semiconductorprecursor; (f) thermal decomposition of the metal oxide semiconductorprecursor to form the metal oxide semiconductor nanomaterial; (g)coating or adhering the hemostatic polymer on the surface of the metaloxide semiconductor nanomaterial; and (h) drying the hemostatic polymercoated or adhered on the metal oxide semiconductor nanomaterial. Theprocess may be conducted in batch, semi-continuous, or continuous mode.

(a) First Aqueous Solution

The process commences by preparing the first aqueous solution comprisinga soluble metal salt A and a soluble metal salt B.

As appreciated by the skilled artisan, the soluble metal salts A and Bare transformed into metal oxide A and metal oxide B after completion ofthe process.

A wide variety of soluble metal salts may be used in the process toprepare metal oxide A and metal oxide B. In various embodiments, solublemetal salt A and soluble metal salt B wherein the metal portion of thesesalts are independently selected from a group comprising an alkalineearth metal, a transition metal, or combinations thereof. Non-limitingexamples of suitable metal portion of alkaline earth metal salts may beberyllium, magnesium, calcium, strontium, or barium. Non-limitingexamples of the metal portion of suitable transition metal salts may bescandium, titanium vanadium, chromium, manganese, iron, cobalt, nickel,copper, yttrium, zirconium, platinum, gold, mercury, niobium, iridium,molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium,hafnium, tantalum, tungsten, rhenium, osmium, any lanthanide, or zinc.

In preferred embodiments, soluble metal salt A and soluble metal salt Bwherein the metal portion of these salts are independently selected froma group consisting of titanium, manganese, nickel, silver, calcium,magnesium, zinc, copper, or combinations thereof.

In particularly preferred embodiments, soluble metal salt A and solublemetal salt B wherein the metal portion of these salts are independentlyselected from a group consisting of zinc, copper, or combinationsthereof.

A wide variety of anions may be used for soluble metal salt A andsoluble metal salt B. An important aspect of these anions is that theanion is readily exchangeable, soluble in aqueous solution, non-toxic,pH neutral, and thermally decomposable. Non-limiting examples ofsuitable anions may be acetate, propionate, any soluble organic salt orcombinations thereof. In a preferred embodiment, the anions used forsoluble metal salt A and soluble metal salt B is acetate.

In other embodiments, the first aqueous solution may further compriseone or more different soluble salts than the soluble salts A and solublesalts B as described above.

The molar ratio of the soluble metal salt A to the soluble metal salt Bmay range from about 12:1 to about 1:12. In various embodiments, themolar ratio of the soluble metal salt A to the soluble metal salt B mayrange from about 12:1 to about 1:12, from about 11:1 to about 1:11, fromabout 10:1 to about 1:10, from about 9:1 to about 1:9, from about 8:1 toabout 1:8, from about 7:1 to about 1:7, from about 7:1 to about 1:7,from about 6:1 to about 1:6, from about 5:1 to about 1:5, from about 4:1to about 1:4, from about 3:1 to about 1:3, or from about 2:1 to about1:2. In a preferred embodiment wherein soluble metal salt A is copperand the soluble metal salt B is zinc, the molar ratio may be about2.3:1.

In general, the concentration of soluble metal salt A, soluble metalsalt B, or combinations thereof in water may range from about 0.01M(moles/liter) to about 1.0M. In various embodiments, the concentrationof the soluble metal salt A and soluble metal salt B may range fromabout 0.01M to about 1.0M, 0.03M to about 0.3M, or from 0.05M to 0.15M.In a preferred embodiment, the concentration of soluble metal salt A,soluble metal salt B, or combinations thereof in water may be about0.15M.

The first aqueous solution may further comprise a stabilizer.Non-limiting examples of stabilizers may be a polyethylene glycol (PEG),polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinylalcohol(PVA), Polyoxyethylene or combinations thereof. In a preferredembodiment, the stabilizer used in the first aqueous solution furthercomprises PEG, specifically PEG4000.

The concentration of the stabilizer in the first aqueous solution mayrange from about 0.0001M to about 0.001M. In various embodiments, theconcentration of the stabilizer in the first aqueous solution may rangefrom about 0.0001M to about 0.001M. In a preferred embodiment, theconcentration of the stabilizer in the first aqueous solution may bepreferably about 0.0007M.

The preparation of the first solution may be achieved by blending thesoluble metal salt A, soluble metal salt B, water, an optionalstabilizer, and an optional solvent in any known mixing equipment orreaction vessel until the mixture achieves homogeneity. These componentsmay be added all at the same time, sequentially, or in any order.

In general, the preparation of the first aqueous solution may beconducted at a temperature that ranges from about 10° C. to about 40° C.In various embodiments, the temperature of the reaction may range fromabout 10° C. to about 40° C., from about 15° C. to about 35° C., or fromabout 20° C. to about 30° C. In one embodiment, the temperature of thereaction may be about room temperature (˜23° C.). The reaction typicallyis performed under ambient pressure. The reaction may also be conductedunder an inert atmosphere or air, for example under nitrogen, argon orhelium.

The duration for preparing the first aqueous solution and will varydepending on many factors, such as the temperature, the method ofmixing, and amount of materials being mixed. The duration of thereaction may range from about 5 minutes to about 12 hours. In someembodiments, the duration of the reaction may range from about 5 minutesto about 30 minutes, from about 30 minutes to about 2 hours, from about2 hours to about 4 hours, from about 4 hours to about 10 hours, or fromabout 10 hours to about 12 hours. In various embodiments, thepreparation may be allowed to continue until the first aqueous solutionobtains homogeneity.

(b) Second Aqueous Solution

The second aqueous solution comprises at least one soluble anion source.An important aspect of these soluble anions is that anion is readilyexchangeable, soluble in aqueous solution, is non-toxic, pH neutral, andthermally decomposable. Non-limiting examples of suitable anion sourcesmay be lithium bicarbonate, sodium bicarbonate, potassium bicarbonate,and ammonium bicarbonate, or any alkaline oxalate, alkaline malate. In apreferred embodiment, the second aqueous solution comprises ammoniumbicarbonate.

The second aqueous solution may be prepared by forming a reactionmixture comprising at least one soluble anion source, water, andoptionally ethanol. These components may be added all at the same time,sequentially, or in any order. The second aqueous solution may beachieved by blending the above components in any known mixing equipmentor reaction vessel until the mixture achieves a clear solution.

In general, the preparation of the second aqueous solution may beconducted at a temperature that ranges from about 10° C. to about 40° C.In various embodiments, the temperature of the preparation may rangefrom about 10° C. to about 40° C., from about 15° C. to about 35° C., orfrom about 20° C. to about 30° C. In one embodiment, the temperature ofthe preparation may be about room temperature (˜23° C.). The preparationtypically is performed under ambient pressure. The preparation may alsobe conducted under air or an inert atmosphere, for example undernitrogen, argon or helium.

The duration for preparing the second aqueous solution and will varydepending on many factors, such as the temperature, the method ofmixing, and amount of the at least one anion source being mixed. Theduration of the reaction may range from about 5 minutes to about 12hours. In some embodiments, the duration of the reaction may range fromabout 5 minutes to about 30 minutes, from about 30 minutes to about 2hours, from about 2 hours to about 4 hours, from about 4 hours to about10 hours, or from about 10 hours to about 12 hours.

Generally, the concentration of the at least one soluble anion source inthe second aqueous solution may range from a concentration of about0.10M to about 1.5M. In various embodiments, the concentration of the atleast one soluble anion source in the second aqueous solution may rangein a concentration from about 0.10M to about 1.5M, from about 0.2M toabout 1.4M, or from about 0.3M to about 1.2M. In a preferred embodiment,the concentration of the at least one soluble anion source in the secondaqueous solution may be about 0.3M.

(c). Preparation of the Insoluble Metal Oxide Semiconductor NanomaterialPrecursor.

The next step in the process is to prepare the insoluble metal oxidesemiconductor nanomaterial precursor. Preparing the insoluble metaloxide semiconductor nanomaterial precursor occurs when the secondaqueous solution comprising the at least one anion source is admixedwith the first aqueous solution. As appreciated by the skilled artisan,once the second aqueous solution is admixed with the first aqueoussolution, a chemical reaction occurs. In a preferred embodiment, themetal oxide semiconductor nanomaterial precursor comprising a copperzinc mixed carbonates are formed and can be depicted according to thefollowing scheme.

As appreciated by the skilled artisan, an advantage of using ammoniumsalt in the second aqueous solution is that by product, ammoniumacetate, is water soluble, easily removed from the metal oxidesemiconductor nanomaterial precursor, neutral pH at room temperature,and trace amount of ammonium acetate are readily thermally decomposed inthe process.

The process may further comprise an organic solvent. The purpose of thesolvent in the process is to reduce the foaming as the two aqueoussolutions are combined, namely carbon dioxide. The addition of solventmay also cause a sudden change of the dielectric constant and change thedynamic of precipitation of the insoluble metal oxide semiconductornanomaterial precursor. These changes may further lead to a hierarchicstructure, a core-shell configuration of the metal oxide semiconductornanomaterial, or combinations of both of properties. An additionalproperty of the solvent is that solvent is volatile so excess amounts ofsolvent may be readily removed. Non-limiting examples of suitablesolvents may be methanol, ethanol, propanol, iso-propanol, acetone orcombinations thereof. In a preferred embodiment, the solvent in theprocess is ethanol.

Generally, the volume percent of the solvent in the mixture of the firstaqueous solution, the second aqueous solution or combinations thereofmay range from about 0.01 volume % to about 0.1 volume % In variousembodiments, the volume percent of the solvent in the mixture of thefirst aqueous solution, the second aqueous solution or combinationsthereof may range from about 0.01 volume % to about 0.1 volume %, fromabout 0.02 volume % to about 0.08 volume %, or from about 0.03 volume %to about 0.07 volume %. In a preferred embodiment, the volume percent ofthe solvent in the mixture of the first aqueous solution, the secondaqueous solution or combinations thereof may be about 0.02 volume %.

The solvent may be added to the first aqueous solution, the secondaqueous solution, or the combination of the first aqueous solvent andthe second aqueous solvent, or combinations thereof.

The metal oxide semiconductor nanomaterial precursor may be prepared byforming a reaction mixture comprising the first aqueous solution, thesecond aqueous solution, and the optional solvent. The metal oxidesemiconductor nanomaterial precursor may be achieved by blending theabove components in any known mixing equipment or reaction vessel orstatic mixer until the mixture achieves completeness of reaction.

In an embodiment, the second aqueous solution may be added to the firstsolution. Generally, the second aqueous solution is added immediately ina batch o by a static mixer continuously in a range from about 20 volume% to about 45 volume % to the first aqueous solution. In a speed from 1to 10 I/min, in various embodiments form 1.25 to 8 l/min. In a preferredembodiment 5 to 6 l/min. This quick addition ensures the chemicalreaction depicted above goes to completion.

Since the insoluble metal oxide semiconductor nanomaterial precursorprecipitates from an aqueous solution, the method of stirring to preparethe precursor is important so amounts of the soluble metal salt A, metalsalt B, or the at least one soluble anion source does not becomeentrained in the insoluble metal oxide semiconductor nanomaterialprecursor. Generally, the process may be stirred mechanically at a speedfrom about 250 rpm (revolution per minute) to about 1000 rpm. In variousembodiments, the stirring speed may range from 250 rpm to about 1200rpm, from about 300 rpm to about 1000 rpm, or from about 500 rpm toabout 900 rpm. Ina preferred embodiment, the stirring speed of theprocess may be about 700 rpm.

In general, the preparation of the insoluble metal oxide semiconductornanomaterial precursor may be conducted at a temperature that rangesfrom about 10° C. to about 65° C. In various embodiments, thetemperature of the preparation may range from about 10° C. to about 65°C., from about 15° C. to about 35° C., or from about 20° C. to about 30°C. In one embodiment, the temperature of the preparation may be aboutroom temperature (˜23° C.). The preparation typically is performed underambient pressure. The preparation may also be conducted under air or aninert atmosphere, for example under nitrogen, argon or helium.

The pH during the addition of the reaction between the second aqueoussolution and the first aqueous solution may range from about 6.0 toabout 8.0. In various embodiments, the pH of the process may range fromabout 6.0 to about 8.0, from about 6.5 to about 7.5, or from about 6.7to about 7.3. In a preferred embodiment, the pH of the process is about6.8 to 7.0.

The duration for preparing the insoluble metal oxide semiconductornanomaterial precursor and will vary depending on many factors, such asthe temperature, the method of mixing, and scale of the process. Theduration of the reaction may range from about 5 minutes to about 6hours. In some embodiments, the duration of the reaction may range fromabout 5 minutes to about 6 hours, from about 15 minutes to about 4hours, or from about 20 minutes to about 1 hour. In a preferredembodiment, the duration for preparing the insoluble metal oxidesemiconductor precursor may be about 30 minutes.

(d) Isolating the Insoluble Metal Oxide Semiconductor NanomaterialPrecursor

The next step in the process is isolating the insoluble metal oxidesemiconductor nanomaterial precursor from the reaction mixture in step(c) comprising water, the stabilizer, and the optional solvent. Asappreciated by the skilled artisan, there are many methods of isolatingthe insoluble metal oxide semiconductor nanomaterial precursor from thereaction mixture in step (c). Non-limiting methods may be filtration,centrifugal separation, decantation, or combinations thereof. Theinsoluble metal oxide semiconductor nanomaterial precursor, afterisolation, may be rinsed with water, ethanol, or combinations thereof.The precursor is washed with water, ethanol, or combinations thereofsolvent until the supernatant is colorless or the precursor colorremains constant.

(e) Drying the Insoluble Metal Oxide Semiconductor Precursor.

The next step in the process is drying the insoluble metal oxidesemiconductor nanomaterial precursor from the reaction mixture in step(d). This step would remove excess amounts of solvent from the insolublemetal oxide semiconductor nanomaterial precursor. As appreciated by theskilled artisan, many devices are available to dry the precursor.Non-limiting examples for drying the solid may be batch driers,convection ovens, rotary dryers, drum dryers, kiln dryers, flash dryers,or tunnel dryers.

In general, the drying of the insoluble metal oxide semiconductornanomaterial precursor may be conducted at a temperature that rangesfrom about 30° C. to about 120° C. In various embodiments, thetemperature of the preparation may range from about 30° C. to about 120°C., from about 40° C. to about 100° C., or from about 50° C. to about80° C. In one embodiment, the temperature of drying may be about 60° C.The preparation typically is performed under ambient pressure. Thepreparation may also be conducted under air or an inert atmosphere, forexample under nitrogen, argon or helium.

The duration for drying the insoluble metal oxide semiconductornanomaterial precursor and will vary depending on many factors, such asthe temperature, the amount of the precursor, and type of the dryer. Theduration of the reaction may range from about 30 minutes to about 48hours. In some embodiments, the duration of the reaction may range fromabout 30 minutes to about 48 hours, from about 1 hour to about 24 hours,or from about 2 hours to about 4 hours. In a preferred embodiment, theduration for drying the insoluble metal oxide semiconductor precursormay be about 3 hours, or until the drying the insoluble metal oxidesemiconductor precursor reaches less than 12% moisture.

(f) Thermal Decomposition of the Insoluble Metal Oxide SemiconductorNanomaterial Precursor Forming the Metal Oxide SemiconductorNanomaterial

The next step in the process is thermal decomposition of the insolublemetal oxide semiconductor nanomaterial precursor forming the metal oxidesemiconductor nanomaterial. This step removes transforms the thermallylabile ligand forming the oxides and removes by-products and impuritiesthat were not removed in step (d). As appreciated by the skilledartisan, carbon, hydrogen and excessive oxygen may be released in formsof carbon dioxide and water steam from the thermally labile ligands,by-products, and impurities. In a preferred embodiment, the metal oxidesemiconductor nanomaterial precursor comprising a copper zinc mixedoxide is thermally decomposed to form the metal oxide semiconductornanomaterial. This reaction can be depicted according to the followingscheme.

In general, thermal decomposition of the insoluble metal oxidesemiconductor nanomaterial precursor may be conducted at a temperaturethat ranges from about 200° C. to about 1000° C. In various embodiments,the temperature of the preparation may range from about 200° C. to about1000° C., from about 225° C. to about 800° C., or from about 250° C. toabout 350° C. In one embodiment, the temperature of drying may be about300° C. The preparation typically is performed under ambient pressure.The preparation may also be conducted under air or an inert atmosphere,for example under nitrogen, argon or helium.

The duration for drying the insoluble metal oxide semiconductornanomaterial precursor and will vary depending on many factors, such asthe temperature, the amount of the precursor, and type of the dryer. Theduration of the reaction may range from about 5 minutes to about 48hours. In some embodiments, the duration of the reaction may range fromabout 10 minutes to about 48 hours, from about 15 hour to about 24hours, or from about 2 hours to about 4 hours. In a preferredembodiment, the duration for drying the insoluble metal oxidesemiconductor precursor may be about 0.3 hour.

The yield of the metal oxide semiconductor material from the processdescribed above may range from 5 to 12 g/L. with high purity.

(g) Coating or Functionalizing the Hemostatic Polymer on the Surface ofthe Metal Oxide Semiconductor Nanomaterial

The process may further comprise coating or adhering a hemostaticpolymer on the metal oxide semiconductor surface. Various hemostaticpolymers are described above. Method for coating or adhering thehemostatic polymer on the metal oxide semiconductor nanomaterial areknown in the arts. In one embodiment, the hemostatic polymer may bedispersed with the metal oxide semiconductor nanomaterial, therebycoating or adhering the hemostatic polymer to the surface of the metaloxide semiconductor nanomaterial.

Generally, the weight % (wt %) of the hemostatic polymer on the metaloxide semiconductor nanomaterial surface may range from about 1 wt % toabout 5 wt %. In various embodiments, the weight % (wt %) of thehemostatic polymer dispersed on the metal oxide semiconductornanomaterial surface may range from about 1 wt % to about 5 wt %, fromabout 2 wt % to about 4 wt %, or from about 2.5 wt % to about 3.5 wt %.In one preferred embodiment, the weight % (wt %) of the hemostaticpolymer on the metal oxide semiconductor nanomaterial surface may beabout 3 wt %.

(h) Drying the Hemostatic Polymer Coated on the Metal OxideSemiconductor Nanomaterial

The process further comprises drying the hemostatic polymer coated oradhered on the surface of the metal oxide semiconductor nanomaterial.This step would remove excess amounts of solvent/water from thehemostatic polymer coated metal oxide semiconductor nanomaterial. Asappreciated by the skilled artisan, many devices are available to drythe precursor. Non-limiting examples for drying the solid may be batchdriers, convection ovens, rotary dryers, drum dryers, kiln dryers, flashdryers, or tunnel dryers.

In general, the drying of the hemostatic polymer coated or adhered onthe metal oxide semiconductor nanomaterial may be conducted at atemperature that ranges from about 30° C. to about 120° C. In variousembodiments, the temperature of the preparation may range from about 30°C. to about 120° C., from about 40° C. to about 100° C., or from about50° C. to about 80° C. In one embodiment, the temperature of drying maybe about 60° C. The preparation typically is performed under ambientpressure. The preparation may also be conducted under air or an inertatmosphere, for example under nitrogen, argon or helium.

The duration for drying the hemostatic polymer coated or adhered to themetal oxide semiconductor nanomaterial surface can and will varydepending on many factors, such as the temperature, the amount of thehemostatic polymer, and the type of the dryer. The duration of thereaction may range from about 30 minutes to about 48 hours. In someembodiments, the duration of the drying may range from about 30 minutesto about 48 hours, from about 1 hour to about 24 hours, or from about 2hours to about 4 hours. In a preferred embodiment, the duration fordrying of the hemostatic polymer coated metal oxide semiconductornanomaterial may be about 3 hours to 6 hours.

(III) Methods for Using the Metal Oxide Semiconductor Nanomaterial

In still another aspect, disclosed herein, encompass methods of usingthe metal oxide semiconductor nanomaterial or the metal oxidesemiconductor nanomaterial surface coated or adhered with the hemostaticpolymer. The methods comprise coating an article such as fabricsbandages, coating textiles, catheters, and syringe needles with themetal oxide semiconductor nanomaterial or the metal oxide semiconductornanomaterial surface coated on or adhered to the hemostatic polymer,hydrophobic coatings comprising the metal oxide semiconductornanomaterial, creams for human and animal use, and photovoltaic cellscomprising the metal oxide semiconductor nanomaterial. These metal oxidesemiconductor nanomaterials may be further incorporated into paints orcoatings.

In one embodiment, the method comprises coating an article such asfabric bandages, textiles, catheters, and needles with an effectiveamount of the metal oxide semiconductor nanomaterial or the metal oxidesemiconductor nanomaterial surface coated or adhered with the hemostaticpolymer. The method comprises dispersing the metal oxide semiconductornanomaterial or the metal oxide semiconductor nanomaterial surfacecoated or adhered with the hemostatic polymer in the appropriate solvent(such as ethanol, water, or combinations thereof), spraying thedispersed metal oxide nanomaterial or the metal oxide semiconductornanomaterial surface coated or adhered with the hemostatic polymer ontothe article thereby forming a coating of the metal oxide semiconductornanomaterial or the metal oxide semiconductor nanomaterial surfacecoated or adhered with the hemostatic polymer on the coating, and dryingthe coating to remove the solvent using heat, vacuum, an inert gas. Oncethe coating is applied to the article, the article providesantimicrobial properties, antibacterial properties, antifungalproperties, or combinations thereof to the article.

In another embodiment, the method comprises mixing the metal oxidesemiconductor nanomaterial or the metal oxide semiconductor nanomaterialsurface coated or adhered with the hemostatic polymer into a topicalcream and then applying the topical cream to a subject to an infectedarea on the subject. With such low toxicity, the topical cream wouldprovide antimicrobial properties, antibacterial properties, antifungalproperties, or combinations to the subject and eliminating the microbe,bacterium, or the fungus.

In still another aspect, the method comprises adding the metal oxidesemiconductor nanomaterial or the metal oxide semiconductor nanomaterialsurface coated or adhered with the hemostatic polymer to a hydrophobiccoating. The method comprises mixing the metal oxide semiconductornanomaterial or the metal oxide semiconductor nanomaterial surfacecoated or adhered with the hemostatic polymer with a hydrophobiccoating. After applying this coating to an article, the coating wouldprovide water repellency and antimicrobial properties, antibacterialproperties, antifungal properties, or combinations to the article.Non-limiting examples of these articles may be metals, glass, andceramics used in many applications.

In yet another embodiment, the metal oxide semiconductor nanomaterialmay be used in photovoltaic cells. The method comprises adding the metaloxide semiconductor nanomaterial into the photovoltaic cell. With such anarrow bandgap, previously described above, photons from light would beabsorbed by the metal oxide semiconductor nanomaterial therebygenerating free electrons and electricity.

In still another embodiment, the metal oxide semiconductor nanomaterialor the metal oxide semiconductor nanomaterial surface coated or adheredwith the hemostatic polymer may be incorporated into various coatingssuch as paints and epoxy resins. After application and drying of thepaints or epoxy resins, the coating would provide antimicrobialproperties, antibacterial properties, antifungal properties, or acombination thereof. These coatings would be useful in a number of areassuch as a hospital, a clinic, food industry, plastic, paints,pharmaceutical industry, or cosmetics industry.

The metal oxide semiconductor nanomaterial may be used for chemicalcatalysis in electrochemical or organic reactions due to its hugesurface area and non-homogenous electrical conduction.

Definitions

When introducing elements of the embodiments described herein, thearticles “a”, “an”, “the” and “said” are intended to mean that there areone or more of the elements. The terms “comprising”, “including” and“having” are intended to be inclusive and mean that there may beadditional elements other than the listed elements.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following examples illustrate various embodiments of the invention.

Example 1: Preparation of the (CuO)1-x/(ZnO)x Nanomaterial

Into a 20 L reactor equipped with mechanical stirring was added 200 gCu(OAc)₂ and 12 L deionized water (DI). To this solution was added 110 gZn(OAc)₂ and 5 g PEG 4000. This mixture was stirred until add the solidsdissolved. Into a 5 L reactor was added 240 g NH₄HCO₃ in 3 L DI water.This mixture was stirred until the solids dissolved. Once the NH₄HCO₃solution becomes homogeneous, the NH₄HCO₃ solution is slowly added intothe 20 L reactor maintaining the mechanical stirring at 200 rpm. Foambegins to form. At this time, 30 mL EtOH is added while the addition ofthe NH₄HCO₃ solution continues. After the addition of the NH₄HCO₃solution is complete, the reaction is stirred for an additional 30minutes where a solid if formed. The solid is filtered using vacuumfiltration. The solid was removed, resuspended in 800 mL of EtOH, andthen filtered. This step was performed an additional time. The solid wasremoved and dried in a vacuum oven at 60° C. for 3 hours.

The solid was removed from the vacuum oven and cooled to roomtemperature. The solid was transferred to flat porcelain cruciblesmaintaining the height of the solid at 1 cm in height. The crucibleswere transferred to a drying oven at atmospheric pressure and the solidwas dried at 130° C. for 1 hour. The oven's temperature was increased to300° C. and the solid is annealed for 20 minutes under a flow ofnitrogen yielding 120 g of the nanomaterial.

Example 2: Preparation of the (CuO)1-x/(ZnO)x Nanomaterial at 0.15M(CuO) when x=0

Into a 2 L reactor equipped with mechanical stirring was added 45 gCu(OAc)₂ and 1.2 L deionized water (DI). To this solution was added 0.5PEG 4000. This mixture was stirred until add the solids dissolved. Intoa 500 mL reactor was added 24 g NH₄HCO₃ in 0.3 L DI water. This mixturewas stirred until the solids dissolved. Once the NH₄HCO₃ solutionbecomes homogeneous, the NH₄HCO₃ solution is slowly added into the 2 Lreactor maintaining the mechanical stirring at 200 rpm. Foam begins toform. At this time, 3 mL EtOH is added while the addition of the NH₄HCO₃solution continues. After the addition of the NH₄HCO₃ solution iscomplete, the reaction is stirred for an additional 30 minutes where asolid if formed. The solid is filtered using vacuum filtration. Thesolid was removed, resuspended in 80 mL of EtOH, and then filtered. Thisstep was performed an additional time. The solid was removed and driedin a vacuum oven at 60° C. for 3 hours.

The solid was removed from the vacuum oven and cooled to roomtemperature. The solid was transferred to flat porcelain cruciblesmaintaining the height of the solid at 1 cm in height. The crucibleswere transferred to a drying oven at atmospheric pressure and the solidwas dried at 130° C. for 1 hour. The oven's temperature was increased to300° C. and the solid was annealed for 20 minutes under a flow ofnitrogen yielding 12.0 g of the nanomaterial.

Example 3: Preparation of the (CuO)1-x/(ZnO)x Nanomaterial at 0.15M(ZnO) when X=1

Into a 2 L reactor equipped with mechanical stirring was added 49.4 gZn(OAc)₂ and 1.2 L deionized water (DI). To this solution was added 0.5g PEG 4000. This mixture was stirred until add the solids dissolved.Into a 500 mL reactor was added 24 g NH₄HCO₃ in 0.3 L DI water. Thismixture was stirred until the solids dissolved. Once the NH₄HCO₃solution becomes homogeneous, the NH₄HCO₃ solution is slowly added intothe 2 L reactor maintaining the mechanical stirring at 200 rpm. Foambegins to form. At this time, 3 mL EtOH is added while the addition ofthe NH₄HCO₃ solution continues. After the addition of the NH₄HCO₃solution is complete, the reaction is stirred for an additional 30minutes where a solid if formed. The solid is filtered using vacuumfiltration. The solid was removed, resuspended in 80 mL of EtOH, andthen filtered. This step was performed an additional time. The solid wasremoved and dried in a vacuum oven at 60° C. for 3 hours.

The solid was removed from the vacuum oven and cooled to roomtemperature. The solid was transferred to flat porcelain cruciblesmaintaining the height of the solid at 1 cm in height. The crucibleswere transferred to a drying oven at atmospheric pressure and the solidwas dried at 130° C. for 1 hour. The oven's temperature was increased to300° C. and the solid was annealed for 20 minutes under a flow ofnitrogen yielding 12.0 g of the nanomaterial.

Example 4: Antibacterial Properties of the (CuO)1-x/(ZnO)x Nanomaterial

A 200 ppm stock suspension of each nanomaterial tested (CuO1-x/ZnOx,CuO, ZnO, mix CuO and ZnO, and Zn doped CuO) were prepared by adding 20mg of particles to 100 mL saline (0.86% NaCl) in a 100 mL volumetricflask. The flask was placed in a sonic bath (Bandelin RK 1028 CH,ultrasonic power 1200 W) and sonicated for 10 minutes.

A bacterial suspension was prepared from cells harvested from a 24 h TSAplate (Tryptic Soya Agar, HiMedia) at 36° C. and suspended in saline.Bacterial concentration in the suspension was measured using anephelometer (PhoenixSpec, BD) and diluted to 10⁶ cfu/mL.

Suspensions in saline of 20 ml nanoparticles and 10 ml of 106 cfu/mLbacteria were mixed to a final volume of 10 mL, in a 50 mL sterilepolypropylene test-tube. The tube was incubated and shaken at a knowntemperature (24° C./36° C.) for 1 hour. At the end of incubation, avolume of 1 mL was taken from the tube and used for preparation ofserial dilutions. 1 mL samples from each dilution were plated withmolten TSA using the pour plate method. Plates were incubated at 36° C.for 1 and 24 hours and counted. Giving a killing about 99.99% for NEDafter 1 h.

Example 5: Preparation of Chitosan Coated Cu_(1-x)O/ZnO_(x)Nanocomposite

This process is conducted in two steps. In the first step, awater-soluble modified chitosan was prepared. The simplest modificationis through synthesis of chitosan mesylate salt or chitosan chloride.Suspend chitosan (1 g) in water (80 ml) at ˜10° C. To this, add methanesulfonic acid or HCl (˜1 mL) dropwise until the solution becomes clearand stir for an additional hour. Resulting modified chitosan waspurified by 48 h dialysis against deionized water.

In the second step, modified chitosan was coated over the nanocomposite.To a suspension of Cu1-xO/ZnOx nanocomposite in deionized water (7.5g/L), add an aqueous solution of the modified chitosan (2.25 g/L) understirring. The solution was stirred for 8 h at room temperature.Excess/unbound polymer was removed by centrifugation and the slurry wasdried under vacuum to obtain chitosan coated Cu1-xO/ZnOx Nanocomposite

Example 6: Preparation of Calcium Alginate Coated on Cu_(1-x)O/ZnO_(x)Nanocomposite

To a suspension of nanocomposite in deionized water (7.5 g/L) was addedan aqueous solution of Na-Alginate (2.25 g/L) dropwise under stirring.Solution was stirred for 8 h at room temperature. Excess/unbound polymerwas removed by centrifugation to obtain Na-Alginate coated nanoparticleslurry. To prepare Ca-Alginate coated nanoparticles, an ion exchangereaction was performed. To the suspension of Na-alginate coatednanoparticles, aq. CaCl₂ (10 g/L) was added dropwise and stirred for 3h. Excess CaCl₂ was removed by centrifugation to get Ca-Alginate coatednanoparticles slurry.

What is claimed is: 1.-15. (canceled)
 16. A metal oxide semiconductornanomaterial composition consistinq essentially of a CuO and ZnOnanomaterial and at least one hemostatic polymer wherein thenanomaterial consists of clusters of CuO and ZnO quantum dots consistingof unions of heterojunctions consisting of n-type metal oxidenanoparticles and p-type metal oxide nanoparticles; wherein thehemostatic polymer is adhered or coated on the metal oxide semiconductornanomaterial; wherein the heterojunctions exhibit an anisotropicconduction of electrons and unequal band gaps; and wherein thenanomaterial exhibits a chemical formula of (CuO)_(1-x)/(ZnO)_(x);wherein x is an atomic ratio of the zinc oxide is in the metal oxidesemiconductor nanomaterial, and wherein x is about 0.2.
 17. The metaloxide semiconductor nanomaterial of claim 16, wherein the metal oxidesemiconductor nanomaterial consists of two regions, where one region isa surface region and the second region is a core region, and the surfaceregion comprises more than 25% by weight of the ZnO and less than 75% byweight of CuO; and the core region comprises less than 10% by weight ofthe ZnO and more than 90% by weight of the CuO A.
 18. (canceled)
 19. Themetal oxide semiconductor nanomaterial composition of claim 16, whereinthe hemostatic polymer consists of chitosan, alginate, gelatin,carboxymethyl cellulose, polyethylene glycol, and combinations thereof.20. The metal oxide semiconductor nanomaterial composition of claim 16,wherein the hemostatic polymer is from about 1 wt % to about 5 wt % ofthe metal oxide semiconductor nanomaterial.
 21. The metal oxidesemiconductor nanomaterial composition of claim 16, wherein thethickness of the hemostatic polymer ranges from about 1.0 nm to about10.0 nm.
 22. The metal oxide semiconductor nanomaterial composition ofclaim 16, wherein the composition exhibits antimicrobial properties,antibacterial properties, antifungal properties, hemostatic properties,and combinations thereof.